Self-spraying artificial snow composition



Patented Nov. 17, 1953 UNED STATES PATENT OFFIC SELF- SPRAYHVGARTIFICIAL SNOW COMPOSITION No Drawing. Application August 31, 1953,Serial No. 377,681

30 Claims.

My invention relates to an improved decorative composition, and moreparticularly, to an improved self-spraying artificial snow formulation.

For some time spray snow," or self-spraying artificial snow has beenavailable commercially, particularly as a Christmas season item. Inessence, the spray snow is a packaged product which contains a suitableflocking agent or material suspended, dispersed or dissolved in apressurized normally gaseous propellant, and the snow is sprayed fromthis package, as desired, through a suitably restricted aperture toobtain a spraying effect from the release of the pressurized gaseouspropellant. As the material is thus sprayed, the flocking agent takesthe form of flocculent snow-like particles which fall upon and generallyadhere to the article or object being sprayed. Certain synthetic resinshave been employed as flocking agents, and the most commonly employedpropellant has been a Freon gas propellant.

Freons are recognized in the art as a class of polyhalogenated loweralkanes used generally as refrigerants. Such alkanes have not more thantwo carbon atoms (i. e., methane and ethane) and are at leasttrihalogenated with the lower molecular weight halogens (i. e., fluorineand chlorine), there being at least one fluorine (F) atom and at leastone chlorine (Cl) atom in the molecule; and these compounds have theformula:

CDCIFXYQn-i) wherein n is an integer from 1 to 2, X is C1 or F, and Y isCl, F or H. Examples: trichloromonofiuoromethane,dichlorodifluoromethane, chlorotrifluoromethane, dichloromonofluoromethane, difluoromonochloromethane, trichlorotrifluoroethane,dichlorotetrafluoroethane, monochloropentafluoroethane, andchlorodifluoromethyl methane, which have boiling points ranging fromabout 30 C. to 50 C.

A gas propellant is, of course, a gas under the conditions of use; inorder to perform its function, it is stored under pressure (as a liquid)and released through an orifice to obtain the propellant effect (as agas). The Freon gas propellants are thus gases at room temperature.

It will, of course, be appreciated that the spray snow packagedformulation requires a rather substantial quantity of the Freon gaspropellant, in order to have an effective spraying or propelling action.On the other hand, the amount of the flocking agent used is acomparatively smaller amount, ranging from the minimum amount that maybe used for practical purposes in order to obtain an appreciablequantity of snow from a given packaged unit to the maximum amount whichmay be used without obtaining a concentration so great that the flockingprocess during spraying is impeded or effectively destroyed. Heretofore,the most suitable commercially available spray snow formulationscontained about 7% acrylic resins and about 93% Freon gas propellant(comprising a mixture of three Freons) As will be appreciated, both theacrylic resins andthe Freon gases are relatively expensive. An attempthas been made to reduce the cost of the aforementioned formulation, bysubstituting phenolic resin for about one-half of the'acrylic resin, butit has beenfound that this formulation has a tendency to undergobubbling instead of flocking when sprayed at a close range. In fact, ithas generally been necessary heretofore to carry out the sprayingoperation from a distance of at least 36 inches in order to effectivelyavoid bubbling. This, also, leaves much to be desired in connection withself-spraying snow formulations. The ingredients used in thesecommercially available snow sprays also have a very distinct odor whichis noticeable during the spraying operation and which is undesirable formany purposes.

It is, therefore, an important object of the instant invention toprovide an improved selfspraying artificial snow formulation.

It is a further object of the instant invention to provide a spray snowwhich flocs without bubbling at very close spraying ranges, which has asubstantially increased quantity of active or solid ingredients perpackaged unit, and/or which permits the use of ingredients aflordingbetter odor control than that heretofore obtainable.

It is a further object of the instant invention to provide an improvedself-spraying artificial snow-forming composition comprising a higherfatty acid as a bulking material, a synthetic resin polymer as aflocking agent, a suitable solvent therefor, and a volatilepolyhalogenated lower molecular weight alkane refrigerant as the gaspropellant. I

, formulation permits the use of a higher solids content. This is a verygreat advantage in most i Stilla further objector the instant inventionI I is to provide i an improved composition compris- I wherein one ofthe radicals R and R. is an alkenyl radical and the other is an alkylradical, Rhas 1 not more than 3 carbon atoms, R has notmore I than 4carbonatoms, an ester wherein R is un-' saturated has a total of 4carbon atoms, and an important aspect or advantage'is thatthe instantcases, whereiniit is more desirable to use low or mini- I mum solidscontent; Whatever thesolids con-f tent, the unique synergistic effectobtained by i I the use of the fatty acid and resin incombinationembodies the various advantages just mentioned, and itpermits the use of high solids when i desired (wherein abcut.5-15% fattyacid is used). In high solids formulations, the preferred ,range forthefatty acid is about 843%, and.

the most preferred amount is about 11%. In low solids formulations, thepreferred range is about to 8-'-10%,'and the'mostpreferred'amount isabout The overlapping proportion of -.8-% between the two preferredproportions ester whereinR is'unsaturated hasa totalof 4-8 carbon atoms.

be sprayed by gas propulsion to form such coating, whichconsistsessentially' of the ingredients of said coating intimatelydispersed in 1 -6 parts ofasuitable solvent.

Other and further objects, advantages, and

features of myinvention will become apparent to those skilled in theartifrom the following detaileddisclosure of preferred embodimentsthere- I 'My invention consists in an improved selfspraying artificialsnow-forming composition" comprising a higher fatty acid as .abulkingmate- I rial, a'synthetic resin polymer as a flocking agent, a suitablesolvent therefor, and a volatile polyhalogenated low molecular weightalkane refrigerant as the propellant, said resin being a polymer of anester having the formula:

wherein one of the radicals R and R is an alkenyl radical and the otheris an alkyl radical, R has not more than 3 carbon atoms, R has not morethan 4 carbon atoms, an ester wherein R is unsaturated has a total of 4carbon atoms, and an ester wherein R is unsaturated has a total of 4-8carbon atoms.

As a bulking agent or material for my composition I have found thehigher fatty acids (1. e., 012-018) to be uniquely superior. Such acidsinclude lauric, myristic, palmitic, stearic, oleic, etc., and the mostpreferred of these is stearic, which gives definitely superior results.The bulking agent is used, as its function indicates, to replace orsupplement a portion of the resin content and for this purpose, it maybe used in amounts ranging from about 2% to about 15% of thecomposition. (As used herein, the term "per cent and "parts mean percentand parts by weight unless otherwise specifled.) Actually, there are anumber of distinct advantages provided by the instant formulation andthese include improved spraying performance (particularly by resistanceto bubbling at close ranges), a whiter snow product, a "fluffler" snowproduct, and an improved odor during spraying (particularly by themasking eflect of the stearic acid upon the somewhat acrid acrylic acidodor). Another particularly A more specific obiectof-the instantinvention v is to provide an improved flocculent sprayed coat- ,ing ofartificial snow consisting essentially of2-15. parts of stearic acid andIVs-8V2 parts of polyc :methylmeth acrylate resin or poiyvinylacetate,resin; and an improved composition adapted to represents the mostpreferred proportion in coma positions. wherein neither extreme of thesolids I contents is desired, although it is still appreciably- ,abovethe solids contents heretofore used.

: 'Asthe resin component, or flockingagent, I

have found certain synthetic resin polymers to p beparticularly'suitable,whereas others are sub I bstantially orwhollyinoperative. 'There'sins of the; invention are olymers of an esterhaving the formula:

' wherein one of the radicals'R and R is an 'al-" p kenyl radical andthe other. is analkyl radical, R has not more than -3 carbon atoms, Rhas not more than 4 carbonatoms, an'ester wherein R is'unsaturated has atotal of 4 carbon atoms, and r an ester wherein-R is unsaturated has a;total of i 48 carbon atoms. I

I Referring to the above definition, it will be seen that the ester isvinylacetate, wherein R is unsaturated and the total number of carbonatoms is consequently four. If R. is unsaturated, then the radical o pat may be methacrylyl or acrylyl, and the radical --O-R' may be methoxy,ethoxy, propoxy or butoxy, B. being an alkyl radical having not morethan 4 carbon atoms. methylmethacrylate and methylacrylate,ethylmethacrylate and ethylacrylate, propylmethacrylate and so on up tobutylmethacrylate. Methylacrylate has a total of four carbon atoms andbutylmethacrylate has a total of eight carbon atoms. Of course, mixturesand copolymers may be used. The acrylic polymers just referred to may bedefined as polymers of an ester having the following formula:

o x-lLo-x' wherein X is an alkenyl radical having not more than 3 carbonatoms and not more than 2 carbon atoms in a chain, and X is an alkylradical hav ing not more than 4 carbon atoms. The most preferred of theacrylic polymers is polymethylmethacrylate resin.

The flocking agent or resin is used. as its function indicates, incombination with the bulking agent to effectively cause suitableflocking of the combined ingredients so as to simulate the texture ofsnow. Again, high, low or medium solids content formulations may beemployed. In general, the flocking agent is used in amounts althoughthere are special situations I Such esters include ranging from about 1%to about 8%% of the composition, and in the high solids formulation, itis used in the range 2 /28 /2% and preferably about 5-7%. Using the mostpreferred resins, such as polymethylmethacrylate and Polyvinylacetate,and the preferred amounts of the bulking agent for the high solidsformulation, it has been found that about 6% resin gives superiorresults.

In the low solids formulation, the preferred amount of resin is about2-5% and most preferably 3%. In a medium solids formulation, about 4-5%is most preferred.

The solvent is used in the instant sprayable composition so as to obtainan intimate mixture or dispersion of the solid ingredients, namely, theresin and the bulking agent, so that such ingredients may be effectivelyborne by the gas propellant on to the article to be covered With theresulting snow-like flocculent product. Preferably, the solvent issufficiently active to effect complete solution of both the solidingredients, and the solvent is, of course, used in an amount sufficientto accomplish the complete dissolving of such ingredients, so as toprovide a single liquid phase which is to be gas-propelled to form thespray. In this single liquid phase, the propellant is, of course,dissolved and the solvent plus the propellant which is miscibletherewith should be capable of dissolving entirely the solids content.Such a solvent may be chlorinated hydrocarbon, an ester, an aromatichydrocarbon, a ketone or even water in some cases. The selection of themost suitable solvent is, in most instances, within the skill of theart, since the solvents for these resins (and fatty acids) are known.Most preferably a volatile solvent, such as acetone, may be used, if nofire hazard is involved, and methylene chloride and/or a non-propellantliquid Freon, such as Freon-11 (trichloromonofiuoromethane) may bepreferred otherwise. The amount of solvent used may range from about toabout 60% of the composition, and about 10-40% is the range for highsolids formulations. The preferred ranges are about 25-30% in a highsolids formulation, about 30-45% in a medium solids formulation, andabout 40-50% in a low solids formulation.

The instant combination of a bulking agent and a flocking resin,intimately dispersed or dissolved in the solvent, is uniquely adapted tobe sprayed by suitable gas propulsion to form a synthetic snow coating,which coating ultimately consists of only the fatty acid bulking agentand the flocking resin, since the solvent will be lost by evaporation.The final coating has distinctly superior fluffy, white snow-liketexture, and may be obtained in the substantial absence of imperfectionsresulting from bubbling, even if spraying is carried out from a veryclose range.

The gas propellant employed is, of course, a Freon refrigerant of thetype hereinbefore described. Most preferably, it is one of theparticularly volatile or low boiling Freons, such asdichlorodifiuoromethane (Freon-12) which has a boiling point of -28 C.It will also be noted that a very substantial portion of the sprayingcomposition consists of the bulking material, the flocking agent and thesolvent, so that a substantially smaller proportion of the gaspropellant need be used in the instant composition. Also, the instantcomposition contains, if desired, at least about twice as much activematerial, which will ultimately result in snow-particle formation, asthose heretofore used.

An example of a preferred high solids formulation for use in the instantinvention is as follows:

11% bulking agent--stearic acid 6% flocking agent polymethylmethacrylateresin 28% solvent-acetone 55% propellantdichlorodifiuoromethan The aboveformulation was suitably packaged and snow spraying therewith, even aclose range of less than 18 inches, resulted in excellent flocking withno bubbling. Substantially, the same results were obtained usingpolyvinylacetate resin in place of the polymethylmethacrylate resin inthe above formulation.

Other formulations which are particularly useful in the practice of theinvention include:

Amount Range Low Solids: Percent Percent (A) Stearic acid 5 3-10 Acrylicresin 3 2-5 Fre0nll.... 46 Freon-l2... 46 Rem.

(ll) S'earlc acid 5 3-10 Acrylic resin 1 3 2-5 Methylene chloride. 4640-50 Freon-l2 46 Rem.

Medium S. llds:

o stearic acid 9 8-10 Acrylic resin 1 4 4-5 Methylene chloride. 31 25-35Fro on-ll l 6 0-10 Freon-l2 50 Rem.

(D) Stcaric aciL 9 8-10 Acrylic resin 1 4 4-5 Methylene chloride. 3730-45 Freon-l2 50 Rem.

(E) stearic acid 8 8-10 Paiyvinylacetate resin 5 4-5 Methylene chloride30 30-45 Freon-l2 57 Ram. High S'ill'lS! (F) Steal-i0 acid 11 843Acrylic resin 1 6 5-7 Methylene chloride 28 25-30 Freon-l2 55 Rem.

1 Acrylic resin: B-72 Acrylic" (Rohn and Haas) or Lucite 46 (DuPom)-polymethylmethacrylatc.

Using each of the foregoing formulations, excellent results are obtainedin the spraying operation and in the resulting snow product.

It will thus be seen that the instant invention permits the use of asmuch as two and onehalf times more active ingredients than were usedheretofore in snow sprays, and the instant invention permits the use ofapproximately onehalf as much Freon than was used heretofore incommercial formulations. In addition, a very substantial amount of theactive ingredients consists of a relatively inexpensive fatty acid,stearic acid, which is substantially less expensive than the acrylicresin. The instant bulking agent, unlike phenolic resins heretoforesuggested, materially assists in the flocking operation by suitablecooperation with the fiocking resin, and in no way impairs the flockingprocess or causes bubbling or other undesirable phenomenon. Also, thepresence of a substantial amount of a solvent which may be selected onthe basis of its characteristic odor, or lack thereof, is present in theinstant formulation so as to reduce appreciably the odor ordinarilyaccompanying snow spraying operations.

It will be understood that modifications and variations may be effectedwithout departing from the scope of the novel concepts of the presentinvention.

This is a continuation-in-part of my application Serial No. 318,953,filed November 5, 1952, entitled Self-Spraying Coating."

I claim as my invention:

1. A composition comprising 5-15% of a C12-C1s fatty acid, 2%;-8 of asynthetic resin polymer, 10-40% of a solvent for the acid and the resin,and the balance consisting essentially of a polyhalogenated lower alkanerefrigerant propellant, said resin being a polymer of an ester selectedfrom the group consisting of vinyl acetate and an ester having theformula:

x-g-o-x' wherein x is a 01-03 alkenyl radical having not more than 2carbon atoms in a chain and X is a C1-C4 alkyl radical.

2. A composition comprising 8-13 of a C111-C1a fatty acid, 5-7% of asynthetic resin polymer. of a solvent for the acid and the resin, andthe balance consisting essentially of a polyhalogenated lower alkanerefrigerant propellant, said resin being a polymer of an ester selectedfrom the group consisting of vinyl acetate and an ester having theformula:

0 x-A-dwherein X is a C2-C3 alkenyl radical having not more than 2carbon atoms in a chain and X is a C1-C4 alkyl radical.

4. A composition comprising 5-15% of a 012-018 fatty acid, 2 /2-8 /2% ofpolyvinylacetate resin as a flocking agent, -40% of a solvent for theacid and the resin, and the balance consisting essentially of apolyhologenated lower alkane refrigerant propellant.

5. A composition comprising 5-15% of a 012-018 fatty acid, 2 -8 ofpolymethylmethacrylate resin as a flocking agent, 10-40% of a solventfor the acidand the resin, and the balance consisting essentially of apolyhalogenated lower alkane refrigerant propellant.

6. A composition comprising 5-15% of stearic acid as a bulking agent, 2/2-8V2% of a synthetic resin polymer, 10-40% of a solvent for the acidand the resin, and the balance consisting essentially of apolyhalogenated lower alkane refrigerant propellant, said resin being apolymer of an ester selected from the group consisting of vinyl acetateand an ester having the formula:

wherein X is a C2C3 alkenyl radical having not more than 2 carbon atomsin a chain and X is a C1-C4 alkyl radical.

7. A composition comprising 5-15% of stearic acid as a bulking agent,/z-8V2% of polymethylmethacrylate resin as a flocking agent, 10-40% of asolvent therefor, and the balance consisting essentially of thedichlorodifluoromethane propellant, the solvent being a solvent for thewherein X is a C2-C3 alkenyl radical having not more than 2 carbon atomsin a chain and X is a C1-C4 alkyl radical, the solvent being a solventfor the acid and the resin, and forming a one-phase liquid system withthe propellant in the composition.

9. A composition as claimed in claim 8 wherein the bulking agent isstearic acid, the flocking agent is polymethylmethacrylate resin and thepropellant is dichlorodifluoromethane.

10. A composition as claimed in claim 8 wherein the bulking agent isstearic acid, the flocking agent is polyvinylacetate resin and thepropellant is dichlorodifluoromethane.

11. A composition as claimed in claim 8 wherein the bulking agent isstearic acid, the flocking agent is polymethylmethacrylate resin, thesolvent is acetone, and the propellant is dichlorodifluoromethanc.

12. A composition as claimed in claim 8 wherein the bulking agent isstearic acid, the flocking agent is polymethylmethacrylate resin, thesolvent is methylene chloride, and the propellant isdichlorodifluoromethane.

13. A self-spraying artificial snow-forming composition having thefollowing formulation: 11% stearic acid, 6% polymethylmethacrylateresin, 28% acetone, and 55% dichlorodifluoromethane.

14. A self-spraying artificial snow-forming composition having thefollowing formulation: 11% stearic acid, 6% polymethylmethacrylateresin, 28% methylene chloride, and 55% dichlorodifluoromethane.

15. A self-spraying artificial snow-forming composition having thefollowing formulation: 5% stearic acid, 3% polymethylmethacrylate resin;46% trichloromonofluoromethane, and 46% dichlorodifluoromethane.

16. A self-spraying artificial snow-forming composition having thefollowing formulation: 9% stearic acid, 4% polymethylmethacrylate resin,31% methylene chloride, 6% trichloromonofluoromethane, and 50%dichlorodifluoromethane.

17. A composition comprising 2-15% of a Cir-C18 acid, 1 /g8 /2% of asynthetic resin polymer. 10-60% of a solvent for the acid and the resin,and the balance consisting essentially of a polyhalogenated lower alkanerefrigerant propellant, said resin being a polymer of an ester selectedfrom the group consisting of vinyl acetate and an ester having theformula:

wherein X is a C2-C3 alkenyl radical having not more than 2 carbon atomsin a chain and X is a C1-C4 alkyl radical.

18. A composition comprising 3-10% of a CIT-C18 fatty acid, 2-5% of asynthetic resin polymer, 40-50% of a solvent for the acid and the resin,and the balance consisting essentially of a polyhalogenatcd lower alkanerefrigerant propellant, said resin being a polymer of an ester selectedfrom the group consisting of vinyl acetate and an ester having theformula:

xJLo-x' wherein X is a C2-C3 alkenyl radical having not more than 2carbon atoms in a chain and X is a C1-C4 alkyl radical.

19. A composition comprising of a Crz-Cza fatty acid, 3% of a syntheticresin polymer, 40-50% of a solvent for the acid and the resin, and thebalance consisting essentially of a polyhalogenated lower alkanerefrigerant propellant. said resin being a polymer of an ester selectedfrom the group consisting of vinyl acetate and an ester having theformula:

0 lat-OJ wherein X is a C2-C3 alkenyl radical having not more than 2carbon atoms in a chain and X is a C1-C4 alkyl radical.

20. A composition comprising 13-10% of a (312-018 fatty acid, 2-5% of apolymethylmethacrylate resin as a flocking agent, 40-50% of a solventfor the acid and the resin, and the balance consisting essentially of apolyhalogenated lower alkane refrigerant propellant.

21. A composition comprising 8'-10% of a C12- Cm fatty acid, 4-5% ofpolymethylmethacrylate resin as a flocking agent, 30-45% of a solventfor the acid and the resin, and the balance consisting essentially of apolyhalogenated lower alkane refrigerant propellant.

22. A composition comprising 12-15% of stearic acid as a bulking agent,lV -8 /2% of a synthetic resin polymer, 10-60% of a solvent for the acidand the resin. and the balance consisting essentially of apolyhalogenated lower alkane refrigerant, said resin being a polymer ofan ester 4 selected from the group consisting of vinyl acetate and anester having the formula:

wherein X is a C2-C3 alkenyl radical having not 5 more than 2 carbonatoms in a chain and X is a C1-C4 alkyl radical.

23. A composition comprising 2-15% of stearic acid as a bulking agent, 1/2-8 /275 of polymethacrylate resin as a flocking agent, 10-60% of a 24.A self-spraying artificial snow-forming composition comprising 340% ofCm-Cia fatty acid as a bulking agent, 2-5% of synthetic resin polymer asa flocking agent. a suitable volatile solvent therefor, and a volatilepolyhalogenated low molecular weight alkane refrigerant as a propellant,said resin being a polymer of an ester selected from the groupconsisting of vinyl acetate and an ester having the formula:

. wherein X is a C2-C3 alkenyl radical having not more than 2 carbonatoms in a chain and X isa C1-C4. alkyl radical, the solvent being asolvent for the acid and the resin, and forming a onephase liquid systemwith the propellant in the composition.

25. A composition as claimed in claim 24 wherein the bulking agent isstearic acid, the flocking agent is polymethylmethacrylate resin and thepropellant is dichlorodifluoromethane.

26. A composition as claimed in claim 24 wherein the bulking agent isstearic acid, the flocking agent is polyvinylacetate resin and thepropellant is dichlorodifluoromethane.

27. A composition as claimed in claim 24 wherein the bulking agent isstearic acid, the flocking agent is polymethylmethacrylate resin, thesolvent is trichloromonofluoromethane, and the propellant isdichlorodifiuoromethane.

28. A self-spraying artificial snow-forming composition comprising 8-10%of a Cia-Cu fatty acid as a bulking agent, 4-5% of a synthetic resinpolymer as a flocking agent, a suitable volatile solvent therefor, and avolatile polyhalogenated low molecular weight alkane refrigerant as apropellant, said resin being a polymer of an ester selected from thegroup consisting of vinyl acetate and an ester having the formula:

x- -o-x' wherein X is a C2-C3 alkenyl radical having not more than 2carbon atoms in a chain and X is a C1-C4 alkyl radical. the solventbeing a solvent for the acid and the resin, and forming a onephaseliquid system with the propellant in the composition.

29. A composition as claimed in claim 28 wherein the bulking agent isstearic acid the flocking agent is polymethylmethacrylate resin and thepropellant is dichlorodifluoromethane.

30. A composition as claimed in claim 28 wherein the bulking agent isstearic acid, the flocking agent is polymethylmethacrylate resin, thesolvent is methylene chloride, and the propellant isdichlorodifluoromethane.

ROBERT J. KERR.

No references cited.

1. A COMPOSITION COMPRISING 5-15% OF A C12-C18 FATTY ACID, 21/2-81/2% OF A SYNTHETIC RESIN POLYMER, 10-40% OF A SOLVENT FOR THE ACID AND THE RESIN, AND THE BALANCE CONSISTING ESSENTIALLY OF A POLYHALOGENATED LOWER ALKANE REFRIGERANT PROPELLANT, SAID RESIN BEING A POLYMER OF AN ESTER SELECTED FROM THE GROUP CONSISTING OF VINYL ACETATE AND AN ESTER HAVING THE FORMULA: 